Antidegradant esters

ABSTRACT

Compounds of the formula ##STR1## wherein, X is from 1 to 12; Z is a member selected from the group consisting of --H, --NH 4 , alkali metal, lower alkyl and lower hydroxyalkyl; R is a member selected from the group consisting of ethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene, styrylene and mixtures thereof; R&#39; is selected from the group consisting of substituted or unsubstituted alkylene, alkenylene, cycloalkenylene, arylene and cycloalkylene moieties containing at least two nuclear carbon atoms and in which any substituent is selected from the group consisting of carboxy, halo and lower alkyl substituents; M is a member selected from the group consisting of hydrocarbon of 1-20 carbon atoms, --RO) x  H, and ##STR2## wherein R, X, R&#39; and Z are as above defined; and P is an integer from 0-1, providing when p is 0, ##STR3## is hydrogen, are non-staining or slightly staining antioxidants possessing antiozonant properties for use as antidegradants in combination with oxidizable organic substrates.

This application is a continuation-in-part of Ser. No. 508,602, filedSept. 23, 1974, now abandoned, which is a continuation of Ser. No.319,101, filed Dec. 27, 1972, now abandoned, which is acontinuation-in-part of Ser. No. 155,297, filed June 21, 1971, nowabandoned.

BACKGROUND OF THE INVENTION

Ideally, any antioxidant for organic substrates containing carbon-carbonunsaturation such as rubber or other plastic material, whether providingprotection in the presence of atmospheric oxygen, ozone or any otheroxidant, should not introduce objectionable characteristics into thesubstrate which make it hazardous to handle, more subject to prematurecuring or weaker physically. The antidegradant should prevent oxidativeattack over extended periods of time without volatilization or change invisual appearance of the organic substrate caused by staining or changein color as by frosting as well as cracking or cutting of the substratesurface.

Antidegradants for use in any substrate subject to change induced byeither chemical or physical action ideally prevent that change forextended time periods without adversely affecting the properties of thesubstrate. Any composite effect derived from the use of a singleantidegradant such as combined heat, light, ageing, oxidation and flexcracking stability, extend the general applicability of thatantidegradant.

Although attack on carbon-carbon unsaturation by ozone may begenerically considered oxidation of the substrate, the intermediateozonides and/or hydroperoxides present a unique problem which is notsolved by antioxidants generally. Thus, antiozonants are a special groupof antidegradents which in themselves may or may not be functionaltoward attack by atmospheric oxygen.

The function of ozone in initiating cracking of rubber has been studiedextensively since 1945. Various antiozonants have been discovered whichextend the useful life of rubber exposed to ozone by extending the timefor initial cracking and retarding the extent of cracking in rubber.Many commercial antiozonants are derived from the N-substitutedparaphenylenediamines.

Those N-substituted para-phenylenediamines prepared by alkylatingpara-aminodiphenylamine with a ketone such as the 4-isopropylaminodiphenylamine are effective antiozonants and do not cause prematurecuring or retard the curing rate when used in rubber. However, the4-alkylaminodiphenylamincs are colored and stain the rubber in whichthey have been incorporated.

Conventionally, anti-oxidants are introduced into rubber in the latexstage. A solid antioxidant is dispersed in the latex to provide adispersion approaching as closely as possible a homogeneous mixturewhile liquid antioxidants are mixed with the latex by emulsification. Atthis point, it is very important that the antioxidant not affectpremature coagulation of the rubber or cause creaming of the latex(rubber destabilization and separation from water in the latex). Afterintroduction of the antioxidant, the rubber is coagulated to separate itfrom the water as an elastomeric dry material. The rubber appears assmall agglomerated masses which are dried by hot air to form crumbs ofrubber. Another addition of antioxidant is conventionally made to thecrumb or to compressed crumb rubber during milling, extruding or otherfabrication treatments.

BRIEF DESCRIPTION OF THE INVENTION

In accordance with this invention, there is provided a group ofantidegradants of the formula ##STR4## wherein X is from 1 to 12;

Z is a member selected from the group consisting of --H, --NH₄, alkalimetal, lower alkyl and lower hydroxyalkyl;

R is a member selected from the group consisting of ethylene,1,2-propylene, 1,2-butylene, 2,3-butylene, styrylene and mixturesthereof;

R' is selected from the group consisting of substituted or unsubstitutedalkylene, alkenylene, cycloalkenylene, arylene and cycloalkylenemoieties containing at least two nuclear atoms and in which anysubstituent is selected from the group consisting of carboxy, halo andlower alkyl substituents;

M is a member selected from the group consisting of hydrocarbon of 1-20carbon atoms, -- RO)_(x) H, and ##STR5## wherein R, X, R' and Z are asabove defined; and p is an integer from 0-1, providing when p is O,##STR6## is hydrogen,

Of these compounds, the preferred classes of antidegradants are those inwhich;

a. R' is selected from the group consistisng of the divalent alicyclicmoieties of cyclopentane, cyclohexane, cyclohexane,bicyclo-(2.2.1)-5-heptene and hydrophenanthrene;

b. those compounds in which R' is an ortho or peri arylene moietyselected from the phenylene and naphthylene nuclei; and

c. those compounds in which R' is a divalent moiety selected from thegroup consisting of alkyl of 2-100 carbon atoms and alkylene andalkenylene radicals of 2 to 24 carbon atoms.

When M is a hydrocarbon of 1-20 carbon atoms it is preferred that saidhydrocarbon be alkyl and cycloalkyl of 1-20 carbon atoms.

The novel antidegradants of this invention are particularly useful whenincorporated into polyolefin compositions such as polyethylene,polypropylene, polybutylene, polybutadiene, polystyrene and copolymersthereof. The polyolefins generally possess molecular weights above 1,000extending upwards into an including molecular weights of 1,000,000. Thepolyolefin may be of the high density, medium density or low densitytype. The polyolefin stabilized with the antidegradants of thisinvention are useful as coating materials as well as thermoplasticmolding compounds. Polyethylene compositions containing theantidegradants of this invention are particularly useful as insulatorsor condensors in electronic equipment.

The compounds of this invention may be used to stabilize lubricants,either the synthetic or petroleum based greases and oils, including thealiphatic esters, polyalkylene oxides, silicones, phosphoric acidesters, silicic acid esters, polyfluorinated hydrocarbons, and the like.Lubricant oils of petroleum origin with which the antidegradant of thisinvention may be incorporated, include the motor oils, transmissionoils, cutting oils, hydraulic oils, and the like, known in the industry.

The compounds of this invention may be incorporated into syntheticgreases such as the alkali metal, alkaline earth and aluminum basegreases in solid or semi-solid gel form.

Furthermore, the compounds of this invention may be added to motor fuelsthat contain saturated and unsaturated blends of hydrocarbon materials.

The compounds of this invention can be incorporated into elastomericcompounds as exemplified by natural and synthetic rubbers such asbutyl-nitrile rubbers, styrene butadiene rubbers, neoprenes,polyisoprenes, polybutadienes, polyisobutylenes, polychlorobutadienesand the like.

Throughout the remaining portion of the disclosure, the discussion andexemplification of the use of the compounds of this invention is madewith specific reference to styrene-butadiene rubber. It is to beunderstood that for the purpose of preventing oxidation either fromatmospheric oxygen or ozone, the compounds of this invention may be usedin a manner known to the stabilizing art in conjunction with anycarbon-carbon unsaturated materials, including waxes and syntheticresins, as well as natural rubber, and especially with the syntheticrubbers of which styrene-butadiene rubber (SBR) is exemplary.

Non-discoloring types of styrene-butadiene rubber generally containeither an aralkyl phosphite or an alkylated or aralkylated phenolic typeantioxidant. The staining types of styrene-butadiene rubber containpara-phenylenediamine type antioxidants, conventionally applied in from0.2 to about 2.5 parts per 100 parts of rubber. Surprisingly, thecompounds of this invention, although derived from the staining typeantioxidants are non-staining or so slightly staining as to producenegligible discoloration in the rubber product. Thus, the excellentantioxidant stabilizing properties of the para-phenylenediamine typeantidegradants are extended into the non-discoloring fluid ofapplication by the compounds of this invention.

The antidegradants of this invention may be employed in acid or esterform to produce dispersions, emulsions or solutions which are mixed withrubber latex during coagulation and protect this latex during subsequenttreatment.

The compounds of this invention need not be added to styrene-butadienerubber in the latex stage but are also applicable as antidegradants whenadded to the rubber crumb or baled crumbs at the mill or otherfabrication stage. Thus, the compounds of this invention may beincorporated into an oxidizable organic substrate containingcarbon-carbon unsaturation, such as styrene-butadiene rubber, in anamount from about 0.01 to about 5 parts per 100 parts of substrate, toafford non-staining to slightly staining compositions with improvedstability toward oxidation by atmospheric oxygen and ozone.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of this invention represent acid esters ofN-oxyalkylenated 4-aminodiphenylamines and N-oxyalkylenated4,4'-diaminodiphenylamines. The amine components of the ester areproduced by known techniques such as is disclosed in U.S. Pat. No.3,330,777. Generally, the 4-aminodiphenylamine or4,4'-diaminodiphenylamine reactant is oxyalkylenated with ethyleneoxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styreneoxide of mixtures thereof to introduce at least one hydroxy alkyl groupto a free amino group thereby producing a secondary or tertiary amine.With the introduction of a basic catalyst and an additional amount ofthe alkylene oxide reactant, the chain length of the N-hydroxyalkylatedgroup may be extended to afford amine or diamine derivatives containingup to about 12 repeating alkoxy groups with one or more terminatinghydroxyl groups.

The N-oxyalkylenated 4-aminodiphenylamine or 4,4'-diaminodiphenylamineintermediate is subsequently esterified with a stoichiometric amount ofa carboxylic acid anhydride to afford the half esters of this invention.When two or more oxyalkylated groups are available for reaction with theanhydride, control of the ratio of reactants enables the production ofcompounds containing the unreacted --RO)_(x) H radical. The performanceof the process for reaction of a dicarboxylic acid anhydride withalcohols of the type involved in theN-oxyalkylenated-4-aminodiphenylamine or 4,4'-diaminodiphenylaminereactants is by known techniques. The free carboxylic acid group of theacid ester so derived, may be converted to the alkali metal salt byreaction with sodium hydroxide or to the ammonium salt by theintroduction of ammonium hydroxide or, it may be converted to a simpleester by the introduction of a monofunctional alcohol such as methanol,ethanol, propanol, butyl alcohol, amyl alcohol, or a lower alkyleneoxide carbonate and the like. Of the carboxylic acid anhydrides employedin the production of the compounds of the instant invention, it ispreferred to employ those acid anhydrides in which the free carboxylicacid, salt or simple ester derivative will provide a sufficient amountof hydrophilicity to assist in the introduction of the antidegradantinto substrate systems containing water or sufficient hydrophobicity totailor the antidegradant compound for use in hydrocarbon and analogousnon-aqueous substrates. Of the carboxylic acid anhydrides those ofspecial interest include the anhydride produced by the Diels-Aldercondensation of maleic anhydride and rosin, phthalic anhydride, maleicanhydride, succinic anhydride, itaconic anhydride, camphoric anhydride,citraconic anhydride, cyclohexane 1,2-dicarboxylic anhydride,cyclohex-4-ene 1,2-dicarboxylic anhydride, 3,4,5,6-tetrachlorophthalicanhydride, cyclopentane 1,2-dicarboxylic anhydride, mellophanicanhydride (1,2,3,4-benzene tetracarboxylic acid), mellitic anhydride(benzene hexacarboxylic acid), trimellitic anhydride, chlorendicanhydride, anhydride products of terpenic like compounds with maleicanhydride, such as β-pinene, dipentene, α-terpinolene and the like.

EXAMPLE 1 N,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

Fifty pounds of para aminodiphenylamine were charged to a reactor andheated to 142° C, with 23 inches of mercury vacuum on the reactor. Thereactor was then sealed and 27 pounds of ethylene oxide were fed to thereactor over a period of 52 minutes at a reaction temperature of142°-172° C. at a rate to moderate pressure buildup. The reaction wasexothermic and cooling was required to hold the temperature in thedesired range. The reaction mixture was allowed to stir for anadditional 19 minutes. The final product, after cooling, was a darkcolored solid exhibiting hydroxyl number of 470, a molecular weight (Mn)of 286, a nil primary amine content, a secondary amine content of 0.34milliequivalents per gram of sample and a tertiary amine content of 3.38milliequivalents per gram of sample.

EXAMPLE 2 N,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

552.6 grams by weight of para-aminodiphenylamine were charged to a2-liter flask equipped with a mechanical stirrer, gas inlet tube forsubsurface additions, a thermometer and a capillary tube immersed in anoil bath as a venting device on the exit side of the flask. The aminewas heated to 133° C and 293.6 grams of ethylene oxide were then addedover a period of 1 hour and 10 minutes at a reaction temperature of133°-174° C. and at a rate to avoid excessive bubbling. Cooling wasrequired to hold the temperature in the desired range. The final cooledproduct was a dark colored solid which exhibited a hydroxyl number of495, a molecular weight (Mn) of 287, a nil primary amine content, asecondary amine content of 0.17 milliequivalents per gram of sample anda tertiary amine content of 3.35 milliequivalents per gram of sample.

EXAMPLE 3 N,N-dihydroxypropyl-N'-phenyl-para-phenylenediamine

552.6 Grams of para-aminodiphenylamine were charged to a 2-liter flaskequipped with a pressure equalized dropping funnel, nitrogen gas inlet,mechanical agitator, thermometer with a thermowatch and a five bulbwater cooled condenser. The para-aminodiphenylamine was heated to 168°C. under a nitrogen gas atmosphere and 357.2 grams of propylene oxidewere added over a period of 7 hours at a rate to avoid excessiverefluxing. The reaction mixture was allowed to stir for an additional 58minutes. The final cooled product was a dark solid exhibiting a hydroxylnumber of 423, a nil primary amine content, a secondary amine content of0.22 milliequivalents per gram of sample, a tertiary amine content of3.23 milliequivalents per gram of sample and a molecular weight (Mn) of308.

EXAMPLE 4 N,N-dihydroxypropoxypropyl-N'-phenyl-para-phenylenediamine

Following the procedure of Example 3,552.6 grams ofpara-amino-diphenylamine were reacted with 697 grams of propylene oxidein the presence of 2.8 grams of anhydrous sodium acetate. The reactionproduct was worked up essentially in the same manner as that of Example3. The final cooled material was a very highly viscous liquid possessinga hydroxyl number of 334, a molecular weight (Mn) of 397, a nil primaryamine content, a secondary amine content of 0.36 milliequivalents pergram of sample and a tertiary amine content of 2.57 milliequivalents pergram of sample.

EXAMPLE 5 Half Ester of Gum Rosin - Maleic Anhydride Adduct andN,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

76.9 Pounds of gum rosin were charged to a reactor and heated under anitrogen atmosphere to 131° C. 24.9 pounds of maleic anhydride wereadded in four parts over a period of 35 minutes to control the reactionexotherm. The temperature of the reaction mixtures rose to 187° C. afterthe second addition and was controlled by cooling. The reaction mixturewas held between 181°-188° C after the maleic anhydride addition for 2hours. 28.1 pounds of N,N-dihydroxyethyl-N'-phenyl-para-phenylenediamineprepared by procedure of Example 1, but exhibiting a nil primarycontent, a secondary amine content of 1.16 milliequivalents per gram ofsample, a tertiary amine content of 2.64 milliequivalents per gram ofsample, a hydroxyl number of 489 and a molecular weight (Mn) of 263 wereadded in three portions. No exotherm was observed. The reaction mixturewas held between 174°-182° C. for 1 hour at which time the mixture wasdischarged from the reactor. The product had an acid number of 226(theory= 219.7) and melted at 110°-124° C.

EXAMPLE 6 Acid Phthalate ofN,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

77 Pounds of the oxyethylated para-aminodiphenylamine of Example 1 at atemperature of 150° C and under a nitrogen gas atmosphere were reactedwith 95.5 pounds of phthalic anhydride in a suitable reactor. Thephthalic anhydride was added in four parts over a 33 minute period tokeep temperature fluctuations at a minimum. The reaction mixture wasallowed to stir for 1 hour and 47 minutes at temperature of 140°-165° Cat which time the mixture was discharged from the reactor. The finalproduct exhibited an acid number of 207 (theory=209.7) and melted at96.4°-104° C.

EXAMPLE 7 Acid Phthalate of N,N-dihydroxypropyl,N'-phenyl-para-phenylenediamine

265.2 Grams (2 hydroxy equivalents) of the product of Example 3 wereweighted into a 1 liter, 3-necked flask and heated under nitrogenatmosphere to 146° C. 296.2 grams (2 moles) of phthalic anhydride wereadded slowly to the reaction vessel at a temperature of 141°-146° C. Thereaction mixture was then held at 141°-155° C for an additional hour atwhich time it was discharged. The final product had an acid number of195.9- 203.7 (Theory=199.9) and melted at 112°-119° C.

EXAMPLE 8 Acid phthalate ofN,N-dihydroxypropoxypropyl-N'-phenyl-paraphenylenediamine

Into a 1 liter flask were placed 335.9 grams (2 hydroxyl equivalents) ofthe oxypropylated para=aminodiphenylamine of Example 4. 296.2 grams (2moles) of phthalic anhydride were introduced into the reaction vesseland the reaction was conducted in the same manner as that presented inExample 7. The final product had an acid number of 184.5 (Theory=177.5)and melted at 103°-106° C.

EXAMPLE 9 Acid Succinate ofN,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

Into a 500 milliliter 3-necked flask equipped with a nitrogen inlettube, glass stirrer, thermometer and a five bulb condenser, wereweighed, 113.3 grams (1.00 hydroxyl equivalent) ofN,N-dihydroxyethyl-para aminodiphenylamine product of Example 2 and100.1 grams (1.00 mole) of succinic anhydride. The reaction wasconducted under a nitrogen blanket with agitation of the reactionmixture. The total reaction time was 1 hour and 49 minutes attemperatures of 142.7°-163.0° C. The final product had an acid number of259.7 (Theory=262.9) and melted at 44°-54° C.

EXAMPLES 10 and 11 Acid Esters of Hexahydrophthalic Anhydride andΔ4-Tetrahydrophthalic Anhydride

Additional acid esters of the N,N-(hydroxyethyl) para-aminodiphenylamineproduct of Example 2 were prepared in accordance to procedures set forthin the preceding example. The reagents, proportions and characteristicsof the resulting products are set forth in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                       Example                                                                       10        11                                               __________________________________________________________________________    Product of Example 2, parts/Wt.                                                                  113.3     56.6                                             Hexahydrophthalic anhydride,                                                  parts by weight    154.2     --                                               Δ .sup. 4 -Tetrahydrophthalic anhydride,                                parts by weight    --        76.0                                             Acid number - Theory                                                                             209.7     211.3                                            Found              241.8     233                                              m.p. ° C.   68-77     75-83                                            Reaction time      1 hr. 46 minutes                                                                        1 hr. 48 min.                                    Reaction temperature ° C.                                                                  147-168.8                                                                              145.1-172.2                                      __________________________________________________________________________

EXAMPLE 12 Acid Chlorendate ofN,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

Into a 1 liter, 3-necked flask were charged 28.3 grams (0.25 equivalentsof OH) of the product of Example 2 and 92.7 grams (0.25 moles) of1,4,5,6,7,7-hexachlorobicyclo [2.2.1]-5-heptene-2,3-dicarboxylicanhydride. To the reaction mixture was added 250 milliliters ofchemically pure acetone. Under a nitrogen blanket and agitation, thereaction was conducted at reflux temperature for 4 hours and 5 minutes.The acetone solvent was removed by vacuum distillation. The finalproduct exhibited an acid number of 137.6 (Theory= 115.9), melted withdecomposition from 136° to 152° C, darkening at 136°-148° C and meltingwith foaming at 148°-152° C.

EXAMPLE 13 Acid 3,4,5,6-Tetrachlorophthalate ofN,N-dihydroxyethyl-N'-phenyl-para-Phenylenediamine

Following the procedure set forth in the preceding example, 28.3 grams(0.25 equivalents of hydroxyl groups) of the product of Example 2 and71.5 grams (0.25 moles) of 3,4,5,6-tetrachlorophthalic anhydride weredissolved in 500 millilters of acetone. The reaction mixture wasrefluxed 4 hours. The product was precipitated by adding the acetonesolution to an excess of distilled water. The product was filtered anddried. The acid number of the product was 185.8 (Theory=140.5). Themelting point was 131°-139° C.

EXAMPLE 14 Acid Maleate ofN,N-dihydroxypropoxypropyl-N'-phenyl-para-phenylenediamine.

168.0 Grams (1.0 equivalents of hydroxyl groups) of the oxypropylatedpara-aminodiphenylamine of Example 4 and 98.1 grams (1.0 mole) of maleicanhydride were charged into a 500 milliliter, 3-necked flask equippedwith a nitrogen gas inlet tube, glass stirrer, thermometer with athermowatch and a five bulb water cooled condenser. The reaction mixturewas heated to 151° C and held for 1 hour at 148°-155° C. The finalproduct melted at 81°-93° C.

EXAMPLE 15 2-Hydroxyethyl Esters of Example 5

A 3-necked flask, equipped with a nitrogen inlet, stirrer, thermometer,and five bulb condenser, containing 300 grams of the product fromExample 5 (1.24 carboxyl equivalents), 3.0 grams potassium carbonate,and 108.7 grams (1.24 moles) of ethylene carbonate were heated to 165°C. This mixture was held at 127°-133° C for 3.5 hours. The solid product(m.p. 71°-82° C.) exhibited a nil acid number.

EXAMPLE 16 2-Hydroxyethyl Esters of Example 6

A 3-necked flask equipped as in Example 16, containing 274 grams (1.0carboxyl equivalent) of the product from Example 6, 2.7 grams potassiumcarbonate, and 88.1 gram (1 mole) ethylene carbonate were heated at165°-168° C for 3 hours and 40 minutes. The solid product melted at55°-67° C. and had a nil acid number.

EXAMPLE 17 Preparation of Methyl Esters

Methyl esters of the acids cited in earlier examples can be prepared bystandard methods. One particularily easy method is as follows:

Take 0.1-0.2 parts of acid to be esterified and dissolve in a 1/1methanol-ether mixture. Add an etheral diazomethane solution, preparedby slowly adding 20 grams of N-methyl-N'-nitro-N-nitrosoguanidine to aliter Erlenmeyer flask containing 400 milliliters of 20 percent KOH and400 milliliters of chilled ether, slowly until a permanent diazomethanecolor persists. Let the solution set 10-15 minutes. The solvent isremoved with a gentle stream of nitrogen leaving the desired methylester.

The antidegradants of this invention were dispersed, emulsified orsolubilized in accordance with known and established procedures andsubsequently added to a rubber latex. Thereafter, salt acid coagulationprocedures were used to prepare dry crumb rubber stocks containing acidantidegradants at the 1,2 or 3 phr (parts per hundred parts rubber)level. For comparative purposes, Flexzone 6-H(N-phenyl-N'-cyclohexyl-p-phenylenediamine) was used as a standardcontrol.

Illustrative of the anti-ageing properties of the antidegradantcompositions of this invention are the compositions based on Example 5,Example 6 and Example 8 cited previously and representing the rosin acidand phthalic derivatized compositions respectively. When incorporatedinto the rubber latex, as described above, coagulated and dried at thelevels shown in Table II, ageing studies were made on the gum rubberstocks thus prepared and the resulting vulcanizate compositions.

Heat ageing studies on the raw gum rubber stocks were carried out bytaking representative samples of dried crumb (SBR) rubber. The rubberwas heat aged in a forced air oven at a temperature of 100° C. for thestated periods of time, represented as days and determining thepercentage of gel formed. Table II illustrates the results of this typeof ageing study with antidegradant compositions. Example 5 (Mix A),Example 6 (Mix B), Flexzone 6-H (Mix C) were added at the 3 phrantidegradant level of addition, and an antidegradant composition basedon Example 8 (Mix D) at the 1 phr antidegradant level of addition.

                  TABLE II                                                        ______________________________________                                        Heat Ageing in Circulating Air Oven at 100° C.                                   Mix A  Mix B    Mix C    Mix D                                      ______________________________________                                        Antidegradant                                                                             3        3        3      1                                        (phr)                                                                         Unaged, % gel   nil      nil    nil    nil                                    Aged,   % gel                                                                         6 day   nil      nil     2.0 nil                                              7 day   nil      5.0    17.0   3.0                                            9 day   4.0      20.0   56.0   20.0                                   ______________________________________                                         nil = less than 1% gel.                                                  

Vulcanizate properties were similarly studied on these same rubberstocks using the procedures and preparations described in ASTMdesignation D15-70 on the vulcanizate formulation shown below.

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        SBR-1500 crumb rubber* 100                                                    Circosol 4240 (napthenic type                                                 processing oil)        25                                                     HAF Black (N-330) (high abrasion                                              furnace carbon black)  62.5                                                   Zinc oxide             3                                                      Stearic acid           1                                                      Sulfur                 1.75                                                   N-t-butylbenzothiazole-2-                                                     sulfenamide            1.25                                                   Mix E - composition from Example 5                                                                   2                                                      Mix F - composition from Example 6                                                                   2                                                      Mix G - Flexzone 6-H   2                                                      ______________________________________                                         *Crumb rubber resulting from the salt acid coagulation technique.        

After compounding and milling, these rubber stocks were cured for 50minutes and 90 minutes at 293° F. to provide samples for the study.Comparisons were made for unaged and aged vulcanizate properties. Theseresults are shown in Table III.

                  TABLE III                                                       ______________________________________                                        Vulcanizate Properties - Unaged and Aged                                                   Mix E   Mix F     Mix G                                          ______________________________________                                        Unaged                                                                         Tensile, psi                                                                   50 minutes   2750      2770      2885                                         90 minutes   2795      2970      2925                                       200% Modulus                                                                    50 minutes   650       790       920                                          90 minutes   740       900       935                                        Elongation, %                                                                   50 minutes   620       520       515                                          90 minutes   560       505       515                                        Aged: 3 days at 100° C.                                                 Tensile, psi                                                                   50 minutes   2810      2735      2815                                         90 minutes   2985      2520      2755                                       200% Modulus                                                                    50 minutes   1605      1900      1305                                         90 minutes   1380      1565      1395                                       Elongation, %                                                                   50 minutes   335       285       415                                          90 minutes   305       305       365                                        ______________________________________                                    

EXAMPLE 18 Preparation of Ammonium Salt of Example 6

374.7 Grams of distilled water and 25.3 grams of concentrated ammoniumhydroxide (28.0-30.0% NH₃) were charged to a 1 liter flask equipped witha mechanical stirrer, thermometer and water cooled condenser. 100 gramsof the pulverized product of Example 6 were added to the reactionmixture under agitation over a 2 minute period. The reaction wasexothermic as evidenced by a temperature rise from 25° to 34.5° C. Thesolution which was filtered and transferred to a bottle was stable.

EXAMPLES 19-23 Preparation of Ammonium Salts

Additional ammoniacal solutions of the acid esters described in theprevious examples were prepared in accordance to procedures set forth inExample 19. The reagents and proportions used are set forth in Table IV

                  TABLE IV                                                        ______________________________________                                                      Examples                                                                      19   20     21     22    23                                     ______________________________________                                        Product of Example                                                                            9      10     11   12    13                                   Parts by weight of                                                                            20     20     20   20    20                                    reactant                                                                     Distilled water - parts                                                                       74.0   74.4   74.6 176.8 75.7                                  by weight                                                                    Ammonium hydroxide                                                                            6.0    5.6    5.4  3.2   4.3                                   (28.0-30.0%                                                                   NH.sub.3)                                                                    ______________________________________                                    

All were clear, dark colored, stable solutions.

EXAMPLE 24 Preparation of Potassium Salts

162 Grams of distilled water and 438 grams of a 2.0182 Normal potassiumhydroxide solution were charged to a suitable reactor. 200 Grams ofpulverized product of Example 6 were added with agitation over a 5minute period. The mixture was agitated to dissolve the resin. Thesolution was filtered but there was no evidence of insoluble material.The final solution exhibited a pH at 26.5° C of 8.86.

The compounds prepared in Examples 18-24 are soluble in latex-wateremulsions and are substantially retained by the rubber upon coagulation.

EXAMPLE 25 Acid Maleate ofN,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine

A mixture of 100 grams (0.681 hydroxyl equivalents) ofN,N-dihydroxyethyl-N'-phenyl-para-phenylenediamine and 66.8 grams ofmaleic anhydride (0.681 moles) were heated under a nitrogen blanket toabout 110°-120° C. for a period of approximately 1.5 hours. The productexhibited a melting point of 90°-92° C. and an acid number of 205.7(229.0 theory).

EXAMPLE 26 ##STR7##

476.7 Grams by weight of N-phenyl-N'-cyclohexyl-p-phenylenediamine wascharged, under vacuum, to a 1 liter pressure reactor and heated to 100°C. The reactor was sealed and the amine was further heated to 156° withagitation. 94 Grams by weight of ethylene oxide was added over an 18minute period at a reaction temperature of 146°-156° C and reactionpressures of up to 102 psig. The reaction mixture was then allowed tostir for an additional 2 hours and 14 minutes at 146°-156° C. until thepressure gauge indicated zero pressure. The final product, aftercooling, was a dark very thick paste exhibiting a nil primary andsecondary amine content and a tertiary amine level of 2.88milliequivalents per gram of sample.

EXAMPLE 27 ##STR8##

343.5 Grams of the oxyethylatedN-phenyl-N'-cyclohexyl-p-phenylenediamine product of Example 26 and 3.4grams of sodium acetate were charged to a 1 liter flask equipped with a500 milliliter pressure equalized dropping funnel, nitrogen gas inlet,mechanical agitator, thermometer with thermowatch and dual water cooledcondensers. Air cooling actuated by a solenoid valve attached to thethermowatch was used to maintain temperatures below 180° C. The aminewas initially heated to 172° C., under a nitrogen gas atmosphere, and433.7 grams by weight of propylene oxide were added over a period of 10hours and 10 minutes to avoid excessive refluxing. The final product,after cooling, was a dark liquid exhibiting a nil primary and secondaryamine content and a tertiary amine content of 1.36 milliequivalents pergram of sample.

EXAMPLE 28 ##STR9##

108.0 Grams by weight of the oxyalkylatedN-phenyl-N'-cyclohexyl-p-phenylenediamine of Example 27 and 22.2 gramsby weight of phthalic anhydride were charged into a suitable reactor (a1 liter flask as equipped in Example 27) and heated under a nitrogenblanket to 147° C. The reaction mixture was maintained at 147°-151° Cfor 1 hour and 35 minutes. The final product, after cooling, was aviscous liquid and had an acid number of 63.1.

EXAMPLE 29

10.0 Grams of the product of Example 28, 5.4 grams of a 2.8928 normalpotassium hydroxide solution and 84.6 grams of distilled water werecharged to a vessel equipped with an agitator. The mixture was stirreduntil all of the product of Example 28 was solubilized. The finalsolution contained a ten percent by weight solution of the product ofExample 28.

EXAMPLE 30

The solution of Example 29 was added to unstabilized SBR latex in anamount sufficient to provide 0.25 and 1.0 parts of antidegradant perhundred parts of rubber (phr). Thereafter, salt acid coagulationprocedures as described in Example 17, were used to prepare dry crumbrubber stock.

The raw gum rubber stocks then subjected to heat ageing tests, asdescribed in Example 17, using samples of the dried stabilized andunstabilized (SBR) rubber. The rubber was heat aged in a forced air ovenat a temperature of 100° C., for a period of time, represented as days,and the percentage of gel formed was calculated. Table V illustrates theresults of this aging study.

                  TABLE V                                                         ______________________________________                                        Heat ageing in circulating air oven at 100° C.                                    % Gel                                                              Sample                                                                              phr    Unaged  1 day   4 days                                                                              5 days                                                                              6 days                               ______________________________________                                        A      0.25  0       0       nil   nil   nil-1.7                              B     1.0    0       0       nil   nil   1.6                                  C     0.0    0       60.5-91.3                                                                             --    --    --                                   ______________________________________                                         nil = less than 1% gel.                                                  

EXAMPLE 31 ##STR10##

410.0 Grams of N-isopropyl-N'-phenyl-p-phenylenediamine was charged to aone liter pressure reactor and, using the procedure of Example 26, 88grams of ethylene oxide was added thereto over a period of 11 minutes ata temperature of 141°-156° C. and pressure of up to 79 psig. Thereaction mixture was maintained at 146°-155° C., with agitation, for anadditional 92 minutes until the pressure gauge indicated a zeropressure. The product, after cooling, was a dark viscous liquid whichshowed signs of crystallization or partial solidification after aprolonged storage (>5 months). Analysis of the product indicated a nilprimary amine content, 0.20 milliequivalents per gram of sample ofsecondary amine and 3.31 milliequivalents per gram of sample of tertiaryamine.

EXAMPLE 32 ##STR11##

82.4 Grams of the product of Example 31 and 44.4 grams of phthalicanhydride were charged to a one liter flask as described in Example 27and heated to 147° C. under a nitrogen atmosphere. The reaction mixturewas maintained at a temperature of 141°-149° C. for a total of 66minutes. The product, after cooling, was a dark solid melting at 78°-88°C. and exhibited an acid number of 123.1.

EXAMPLE 33

20.0 Grams of the product of Example 32, 21.2 grams of 2.8928 normalpotassium hydroxide and 158.8 grams of distilled water were charged to avessel and stirred until a solution resulted containing 10 percent byweight of the product of Example 32.

EXAMPLE 34

The product of Example 33 was incorporated into SBR rubber and tested atthe 0.25 phr level of product as described in Example 30. The results ofthe heat ageing study showed a 0,0, nil, 0,0, nil and 0 gel contentafter 1,2,3,4,5,6 and 7 day, respectively, heat ageing at 100° C.

EXAMPLE 35 ##STR12##

8105 Grams of p-aminodiphenylamine was charged to a reactor and heatedto 101° C under a vacuum of 29 inches of mercury. The reactor was thensealed and 11.3 pounds of propylene oxide were fed to the reactor over a2 hour and 38 minute period at temperatures up to 146.2° C and pressuresup to 18 psig. The reaction mixture was thereafter stirred for anadditional 17 minutes during which time the pressure in the reactordropped to zero psig. The reactor was opened and 40.5 grams of anhydroussodium acetate was added under 24 inches of mercury vacuum. The reactorwas sealed and an additional 11.3 pounds of propylene oxide was fedthereto over a 2 hour and 4 minute period at temperatures of148.8°-157.5° C. and pressures up to 23 psig. An additional 12 minutestirring period was required to digest the propylene oxide to 0 psig.

The final product was a dark liquid whose viscosity was found to be26,600 poises at 25.7° C. The weight per gallon of this material was9.03 pounds, the primary amine content was nil, the secondary aminecontent was found to be 0.16 milliequivalents per gram of sample whilethe tertiary amine content was found to be 2.32 milliequivalents pergram of sample. The final product contained 4 moles of propylene oxideper mole of p-aminodiphenylamine.

EXAMPLE 36 ##STR13##

p-aminodiphenylamine was oxypropylated by the procedure of Example 35 toyield a material containing 8 moles of propylene oxide per mole of theamine. The final product showed a nil primary amine content, a secondaryamine level of 0.11 milliequivalents per gram of sample and a tertiaryamine content of 1.48 milliequivalents per gram of sample. The finalproduct exhibited a viscosity at 25.1° C. of 179.6 poises and a weightper gallon of 8.82 pounds.

EXAMPLE 37 ##STR14##

208.4 Grams of the product of Example 36 and 350.7 grams ofisooctadecenylsuccinic anhydride were charged to a suitable reactor andheated under a nitrogen atmosphere to 150° C. The reaction mixture washeld at 147°-150° C. for a period of 76 minutes. The final product,after cooling, was a dark viscous liquid having an acid number of 97.2.

EXAMPLE 38

The product of Example 37 was incorporated into SBR 1500 rubber byprocedures described in Examples 29 and 30 at the 0.25 and 0.50 phrlevels. Heat ageing studies carried out by procedure described inExample 30 gave the results as tabulated in Table VI.

                                      TABLE VI                                    __________________________________________________________________________    % Gel After 100° C Heat Aging For:                                     DAYS                                                                          PHR 4   5   6   7   8   9   10  11                                            __________________________________________________________________________     0.25                                                                             0.0 0.0 0.0 1.8 --  --  --  --                                            0.25                                                                              0.0 0.0 0.0 0.8 --  --  --  --                                            0.50                                                                              0.0 0.5 0.2 3.3 2.9 3.5 5.6 12.0                                          __________________________________________________________________________

EXAMPLE 39 ##STR15##

208.3 Grams of the product of Example 35 and 266.3 grams ofdodecenylsuccinic anhydride were heated together in a suitable reactorunder a nitrogen atmosphere to 151.7° C. The reaction mixture was heldfor 61 minutes at 148.8°-151.7° C. The final product, after cooling, wasa dark low melting solid with an acid number of 116.2.

EXAMPLE 40 ##STR16##

52.1 Grams of the product of Example 35 and 276.1 grams of a C50 alkylsubstituted succinic anhydride were heated together in a suitablereactor under a nitrogen atmosphere to 147° C and held at 147°-148.1° Cfor a period of 63 minutes. The product, after cooling, was a dark,viscous liquid with an acid number of 35.7. The product, whenincorporated into SBR rubber according to procedures of Examples 29 and30 at a 0.25 phr level, acted as an antidegradant. Gel content, of therubber containing this product, was zero after 1 day at 100° C. and only1.3% after a 2 day heat ageing period in a 100° C air circulating oven.

EXAMPLE 41 ##STR17##

98.1 Grams of maleic anhydride and 141.9 grams of β-pinene (96% pure)were charged to a suitable reactor and heated under a nitrogenatmosphere to 146.8° C. The reaction was exothermic and some cooling wasnecessary. The reaction mixture was held at 143.8°-146.8° C. for a 11/2hour period. The mixture was then heated to 199.5° C and held for anadditional 11/2 hour period at 197°-202° C. The product, after cooling,was a waxy solid which contained about 1% unreacted maleic anhydride byNMR analysis. The acid number of the product was 483.2 and the molecularweight was found to be 245.

EXAMPLE 42 ##STR18##

417.5 Grams of product, prepared as described in Example 41, was heatedin a suitable reactor under a nitrogen atmosphere to 116.7° C. 409.7grams of the product of Example 35 was charged to a pressure equalized,heated, dropping funnel and heated to 115°-125° C., then added to thereactor over a 10 minute period. The reaction was exothermic and coolingwas necessary to maintain a temperature below 129° C. The reactionmixture was then held for 6 hours at 121.5°-128° C. The product, aftercooling, was a dark solid, melting between 68° and 78° C., and exhibitedan acid number of 121.0. The molecular weight of this material was foundto be 862.

EXAMPLE 43 ##STR19##

333.0 Grams of a product prepared by the procedure of Example 41 wasreacted with 450.3 grams of the product of Example 36 at 122°-129° C.under a nitrogen atmosphere for 3 hours. The product, after cooling, wasan extremely viscous liquid and exhibited an acid number of 100.7.

EXAMPLE 44 ##STR20##

184.2 Grams of paraaminodiphenylamine was charged to a 500 milliliterflask equipped with a gas inlet tube, a pressure equalized additionfunnel, a mechanical agitator, a thermometer with a thermowatch and awater cooled condenser. The amine was heated to 104° C. and 11.5 gramsof hydrogen chloride gas were added over a 13 minute period. Thereaction was exothermic and the temperature rose to 165.2° C. 79.9 Gramsof 2,3-butylene oxide was added to the reaction mixture over a 19 minuteperiod. Refluxing resulted and the temperature dropped from 113.2° C. atthe start of the addition, to 78.5° C. at the end of the addition.Heating was continued for approximately 14 hours until refluxing hadceased. 33.9 Grams of anhydrous sodium carbonate were added at 124° C,refluxing resumed, and the reaction mixture was heated for approximately11 hours. The final product was filtered (hot) through a glass frittedfunnel. Amine analysis of the final product gage the following:

    __________________________________________________________________________    Total Amine                                                                   Calc'd         = 3.70                                                                             milliequivalents/g of sample                              Found   = 3.69 "                                                              Primary Amine  = 0.70                                                                             "                                                         Secondary Amine                                                                              =2.84                                                                              "                                                         Tertiary Amine = 0.15                                                                             "                                                         __________________________________________________________________________

EXAMPLE 45 ##STR21##

98.5 Grams of the product of Example 44 was charged to a suitablereactor and heated to 165° C. under a nitrogen atmosphere. 0.74 grams ofsodium methylate was added thereto. 70.2 Grams of ethylene oxide wasthen added subsurface to the reaction mixture over a period of 41minutes at temperatures of 159°-180.5° C. The final product exhibitedthe following amine analysis.

    __________________________________________________________________________    Total Amine                                                                   Calc'd         = 2.16                                                                             milliequivalents/g of sample                              Found   = 2.13 "                                                              Primary Amine  = 0.08                                                                             "                                                         Secondary Amine                                                                              = 1.46                                                                             "                                                         Tertiary Amine = 0.59                                                                             "                                                         __________________________________________________________________________

EXAMPLE 46 ##STR22##

90.4 Grams of the product of Example 45 and 29.6 grams of phthalicanhydride were reacted as shown in Example 32. The final product, aftercooling was a dark solid having an acid number of 93.5

EXAMPLE 47 ##STR23##

99.6 Grams of 4,4'-diaminodiphenylamine was charged to a suitablereactor and heated under a nitrogen atmosphere to 170° C. 130.2 grams ofpropylene oxide were added to the amine over a 53/4 hour period at148°-179° C. Some refluxing of the oxide occurred during the addition.57.4 grams of the resulting oxypropylated 4,4'-diaminodiphenylamine and133.0 grams of dodecenylsuccinic anhydride were then charged to asuitable reactor and heated to 150° C. for 1 hour, under a nitrogenatmosphere with agitation. The final product, after cooling, was a darksolid, melting in a range of 94°-104° C, having an acid number of 128.2.

SBR rubber crumbs containing 0.25 phr of the final product showed no gelafter a 1 day 100° C. heat ageing period and only 2.8% gel content aftera 2 day heat ageing period at 100° C.

EXAMPLE 48 ##STR24##

184.2 Grams of para aminodiphenylamine is charged to a suitable reactorand heated to 175°-180° C under a nitrogen atmosphere. 240.3 grams ofstyrene oxide is added so as to prevent excessive refluxing. The mixtureis then heated at 175°-180° C. until all of the oxide has reacted asevidenced by cessation of the reflux. The final product has a totalamine value of 2.36 milliequivalents per gram of sample.

EXAMPLE 49 ##STR25##

296.2 Grams of phthalic anhydride is reacted with 424.5 grams of theproduct of Example 48 in the manner of Example 12. The product exhibitsan acid number of 155.7.

EXAMPLE 50 ##STR26##

282.6 Grams of B-pinene (96% pure) was charged to a suitable reactor andheated under a nitrogen atmosphere to 140° C. 196 grams of ground maleicanhydride was added to the reactor over a 3 minute period. The reactionwas exothermic and the temperature rose to 158° C. The reaction mixturewas held for 43/4 hours at temperatures of 145°-158° C. NMR analysis ofthe reaction mixture showed the unreacted maleic anhydride level at5.4%. 268.7 Grams of molten oxyethylated para aminodiphenylamine,prepared by process described in Example 1, was added to the reactionmixture at a temperature of about 100° C. The molten amine was added asquickly as it could be poured. The reaction was exothermic and thetemperature rose to 156° C. within 2 minutes. The final product, aftercooling, was a dark solid, melting in the 60°-70° C. range, andexhibited an acid number of 134.9.

EXAMPLE 51 ##STR27##

135.0 Grams of N-isopropyl-N'-phenyl-p-phenylenediamine, which had beenethoxylated by the method of Example 31, and 128.5 grams oftetrapropenylsuccinic anhydride were charged to a 500 milliliter flaskequipped as described in Example 14. The condenser was not water cooled.The reaction mixture was heated to 133°-140.8° C for approximately 63minutes under a nitrogen atmosphere. The final product, a solid,exhibited an acid number of 97.0 (Theory=104.5) and melted in a 45°-55°C. range.

EXAMPLE 52 ##STR28##

137.6 Grams of N-isopropyl-N'-phenyl-p-phenylenediamine, which had beenethoxylated by the method of Example 31, and 175.2 grams ofisooctadecnylsuccinic anhydride were charged to a 500 milliliter flaskequipped as described in Example 39 and heated to 134°-135° C, for 1hour, under a nitrogen atmosphere. The final product, a viscous liquid(approx. 29,800 poises at 24° C) exhibited an acid number of 87.8(Theory=89.7).

EXAMPLE 53 ##STR29##

137.8 Grams of N-isopropyl-N'-phenyl-p-phenylenediamine, which had beenethoxylated by the method of Example 31, and 1.4 grams of sodiummethoxide were charged to a one liter reaction flask, equipped with a500 milliliter pressure equalized dropping funnel, nitrogen gas inlet,mechanical agitator, thermometer with thermowatch and dual water cooledcondensers. The ethoxylated amine was initially heated to 175° C under anitrogen atmosphere. 218.2 Grams of propylene oxide were charged to thepressure equalized funnel. The oxide was added, over approximately a 7hour period, at such a rate as to prevent excessive refluxing of theoxide at 167°-178° C. The reaction vessel was weighed after the oxideaddition was completed and it was found that 202.2 g. of propylene oxidehad reacted with the amine. The final product was a liquid with aviscosity of 32.4 poises at 23° C.

EXAMPLE 54 ##STR30##

135.8 Grams of the product, prepared in Example 53, and 29.6 grams ofphthalic anhydride were charged to a 250 milliliter flask, equipped asin Example 39, and heated under a nitrogen atmosphere to 149.5° C. Thereaction mixture was held at 148°-149.5° C for 62 minutes. The finalproduct, a viscous liquid (13,600 poises at 23.5° C), exhibited an acidnumber of 68.2 (Theory=67.8).

EXAMPLE 55 ##STR31##

135.8 Grams of the product of Example 53 and 52.4 grams oftetraprepenylsuccinic anhydride were reacted together for 1 hour at134°-136° C under a nitrogen atmosphere in a suitable reactor. The finalproduct, a viscous liquid (1830 poises at 23.5° C) exhibited an acidnumber of 65.2 (Theory=59.6).

EXAMPLE 56 ##STR32##

208.3 Grams of product prepared by the process of Example 35, with theexception that it was prepared in a flask at atmospheric pressure, and236.5 grams of N-decenyl succinic anhydride were heated together in asuitable reactor, under nitrogen, to about 146° C. The reaction mixturewas held for 118 minutes at 145°-146° C and the final product exhibitedan acid number of 119.9 with a viscosity of 55,400 poises at 23.2° C.

EXAMPLE 57 ##STR33##

208.3 Grams of product prepared by the process of Example 35, with theexception that it was prepared in a flask at atmospheric pressure, and262 grams of N-dodecenyl succinic anhydride were heated together in asuitable reactor, under nitrogen, to about 146° centigrade. The reactionmixture was held for 115 minutes at about 144.8°-146° C and the finalproduct exhibited an acid number of 122.2 with a viscosity of 4,770poises at 80° C.

EXAMPLE 58 ##STR34##

208.3 Grams of product prepared by the process of Example 35, with theexception that it was prepared in a flask at atmospheri pressure, and320.5 grams of N-hexadecenyl succinic anhydride were maintained at about143°-145° C for forming, under nitrogen. The final product exhibited anacid number of 105.7 and a viscosity of 4,190 poises at 23.8° C.

EXAMPLE 59 ##STR35##

208.3 Grams of product prepared by the process of Example 35, with theexception of Example 46, and 346.8 grams of isooctadecenyl succinicanhydride were maintained at about 144°-146.5° C for 68 minutes undernitrogen. The final product exhibited an acid number of 100.8 andviscosity of 15,800 poises at 23.8° C.

EXAMPLE 60 ##STR36##

208.3 Grams of product prepared by the process of Example 35, with theexception of Example 46, and 347.8 grams of N-octadecenyl succinicanhydride were maintained at about 144.8°-145° C for 127 minutes, undernitrogen. The final product exhibited an acid number of 100.8 andviscosity of 33,600 poises at 23.5° C.

EXAMPLE 61 ##STR37##

336.4 Grams of product prepared by the process of Example 27 and 45.7grams of maleic anhydride were maintained at about 99°-100° C for 1hour. The final product exhibited an acid number of 65.8 and viscosityof 7,140 poises at 24° C.

We claim:
 1. A compound of the formula ##STR38## wherein, X is from 1 to12; Z is a member selected from the group consisting of --H, --NH₄,alkali metal, lower alkyl and lower hydroxyalkyl; R is a member selectedfrom the group consisting of ethylene, 1,2-propylene, 1,2-butylene,2,3-butylene, styrylene and mixtures thereof; R' is selected from thegroup consisting of substituted or unsubstituted arylene moietiesderived from an aryl dicarboxylic acid anhydride and in which anysubstituent is selected from the group consisting of carboxy, halo andlower alkyl substituents; M is a member selected from the groupconsisting of alkyl and cycloalkyl hydrocarbon of up to 20 carbon atoms,--RO)_(x) H, and ##STR39## wherein R, X, R' and Z are as above defined;and p is an integer from 0-1, providing when p is O, ##STR40## ishydrogen.
 2. The compound of claim 1 wherein ##STR41## is hydrogen. 3.The compound of claim 1 wherein R' is phenylene or naphthalene.
 4. Thecompound of claim 3 of the formula: ##STR42##
 5. The compound of claim 3of the formula: ##STR43##
 6. The compound of claim 3 of the formula:##STR44##
 7. The compound of claim 3 of the formula: ##STR45##
 8. Thecompound of claim 3 of the formula: ##STR46##
 9. 9. compound of claim 3of the formula: ##STR47##
 10. The compound of claim 3 of the formula:##STR48##
 11. The compound of claim 3 of the formula: ##STR49##
 12. Thecompound of claim 3 of the formula ##STR50##
 13. The compound of claim 3of the formula ##STR51##